Alkenyl halolactone esters and acids and lubricants containing them

ABSTRACT

Alkenyl halolactone esters of monools and polyols are described. These materials are useful as lubricating oil detergency and/or dispersancy additives.

United States Patent 1 1 Kennedy et al.

ALKENYL HALOLACTONE ESTERS AND ACIDS AND LUBRICANTS CONTAINING THEM inventors: Brian R. Kennedy, San Rafael;

Warren Lowe, El Cerrito, both of Calif.

Chevron Research Corporation, San Francisco, Calif.

Filed: Aug. 5, 1971 Appl. No.: 169,544

Assignee:

U.S. Cl 252/54.6, 252/56 D, 260/3436 Int. Cl. Cl0|n 1/26, ClOm l/30 Field of Search 252/54.6, 56 D; 1 260/3436 Aug. 28, 1973 Krukziener 252/56 D Primary Examiner-Daniel E. Wyman Assistant Examiner-W. H. Cannon Attorney-J. A. Buchanan, Jr., C. J. To'nkin and G. F. Magdeburger [57] ABSTRACT Alkenyl halolacto ne esters of monools and polyols are described. These materials are useful as lubricating oil detergency and/or dispersancy additives. 1

15 Claims, No Drawings ALKENYL HALOLACTONE ESTERS AND ACIDS AND LUBRICANTS CONTAINING THEM BACKGROUND OF THE INVENTION 1. Field of the Invention This invention concerns novel alkenyl halolactone esters of monools and polyols and lubricating oil compositions containing those esters as metal-free (ashless") detergent or dispersant additives.

It has long been recognized that lubricating oils designed for use in internal combustion engines should possess significant detergency or dispers ancy characteristics. This is necessary so that the deposits of varnish and sludge which would otherwise accumulate on pistons, cylinder walls, crankcases and other surfaces within the engine will be minimized. Accumulation of such deposits adversely affects the efficient operation of the engine. This reduced efficiency in turn results in excessive pollutant emissionsby the engine,-reduced power and reduced engine life.

Early lubricating oil detergent and dispersant additives were metal-containing compounds such as metal sulfonates. These left an undesirable residue or ash" in the engine. More recently, there have been developed a number of so-called ashless additives which contain no metal. These are exemplified by the widely used alkenyl succinimides. There is a constant need in the lubricant industry for ashless detergents and dispersants which combine the properties of high detergency or dispersancy, low cost, good oil solubility and ease of preparation.

2. Description of the Prior Art Amide derivatives of alkyl substituted lactone esters are described in US. Pat. No. 3,200,075.

SUMMARY We have now discovered an. effective ashless. detergent/dispersant additive which consists of the reaction product of (l) a monool or polyol and (2.) an alkenyl chlorolactone or bromolactone alkyl ester or acid which has been prepared by the reaction of alkenyl succinic anhydride, chlorine or bromine, and a low molecular weight alkanol or water. The invention also encompasses the lubricant compositions comprising an oil of lubricating viscosity and the described additive.

DETAILED DESCRIPTION OF THE INVENTION The compositions of this invention are novel metalfree (ashless) lubricating oil detergency/dispersancy additives and lubricants containing those additives. These lubricants provide excellent detergency and/or dispersancy in both diesel and gasoline internal combustion engines. Iln diesel engine tests in which the engine is operated under extremely severe conditions, these lubricants have proved to be quite efi'ective in: maintaining a low level of deposits: in the engines. The

additive imparts to the lubricant a number of desirable properties, as illustrated in the examples below.

PREPARATION OF THE COMPOSITIONS.

The additive composition, of this invention is the reaction product of a monool or polyol and an alkenyl chlorolactone or bromolactone alkyl ester oraci'd. The ester or acid is prepared by reacting an alkenyl succinic.

anhydride, chlorine or bromine, and a low molecular weight alkanol or water, respectively.

wherein R is an alkenyl group most conveniently obtained by polymerizing an olefin or mixture of olefins containing from about two to five carbon atoms. The molecular weight of the resulting polymer will generally be in the range of about 400 to 3,000 and more usually in the range of about 700 to 1,400. Useful olefins are illustrated by ethylene, propylene, l-butene, Z-butene, isobutene, l-pentene and mixtures thereof, preferably isobutene. The methods of polymerizing such olefins to polymers of the designated molecular weight are well known in the art and do not require exemplification here. (See, for example, US. Pat. Nos. 3,024,195 and 3,018,250.)

The alkenyl succinic anhydride is converted to the alkenyl chloroor bromolactone alkyl ester or acid by reaction in solution with chlorine or bromine and, for the ester, a low molecular weight alkanol, or, for the acid,.water. The low molecular weight alkanols are those containing one to three carbon atoms and no functional groups other than a single hydroxy group. The alkanols thus include methanol, ethanol, 1-

propanol, and 2-propanol. Of these methanol and ethanol (particularly methanol) are preferred.

The halogens which may be used to produce the alkenyl halolactone ester or acid are chlorine and bromine The remaining halogens, fluorine and iodine, generally do not give satisfactory reaction products. The chlorine is usually present as chlorine gas, which is bubbled through the reaction mixture. Bromine is present as liquid in the reaction mixture. Alternatively, one may use a compound which will donate chlorine or bromine (such as N-bromosuccinimide) but which will otherwise not participate to any significant degree in the reaction of the anhydride, alkanol and chlorine or bromine. The residue of such a compound should also be readily separable from the reaction mixture.

The reaction of anhydride, chlorine or bromine, and

alkanol or water is ordinarily carried out at ambient reaction is slightly exothermic. If desired, cooling.

means may be provided to maintain the reaction mixture at a temperature at or slightly above ambient temperature. Following reaction the solvent and excess reactants are removed and the product recovered.

The alkenyl halolactone alkyl ester or acid product will generally contain about 1-8 weight percent chlorine or bromine. The infrared spectrum of the product will show distinctive peaks at about l,775-l,780 cm (lactone) and about 1,740 cm (ester) or about 1,700 cm (acid). I

The alkenyl halolactone alkyl ester or acid and the monoor polyol are reacted with heating to a temperature in the range of l70-l90 C. for a period of l-24 hours. The reaction is conducted in the presence of a small amount of hydroxide anion and under a nitrogen or other inert gas atmosphere. Usually approximately equimolar amounts of reactants are used, although a small excess of monoor polyol may be used if desired. The esterification or transesterification reaction may be caused to proceed to completion by removal during the reaction of the low molecular weight alkanol or water produced. The product may be recovered by conventional means, including separation of unrcacted monoor polyol, which may be recovered.

The monools or polyols which are useful in the above-described esterification or transesterification reaction may be selected from any of the following: l) aliphatic or alicyclic monohydric and polyhydric compounds, either saturated or unsaturated, and (2)'aromatic monohydric or polyhydric compounds. Preferred are the polyhydric compounds having 'at least three hydroxyl groups. Also preferred are those monohydric or polyhydric compounds containing only carbon, hydrogen, and oxygen atoms.

The aliphatic or alicyclic alcohols from which the esters may be-derived preferably contain up to about 40 aliphatic carbon atoms. They may be monohydric alcohols such as methanol, ethanol, isooctanol, dodecanol, cyclohexanol, cyclopentanol, behenyl alcohol, hexatriacontanol, neopentyl alcohol, isobutyl alcohol, benzyl alcohol, B-phenylethyl alcohol, 2- methylcyclohexanol, monomethyl ether of ethylene gylcol, monobutyl ether of ethylene glycol, monopropyl ether of diethylene glycol, monododecyl ether of triethylene glycol, monooleate of ethylene glycol, monostearate of diethylene glycol, sec.-pentyl alcohol, tert.-butyl alcohol, and dioleate of glycerol.

The polyhydric alcohols preferably contain from 2 to about hydroxyl groups. They are illustrated by ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol, and other alkylene glycols in which the alkylene group contains from two to about eight carbon atoms. Other useful polyhydric alcohols include glycerol, monooleate of glycerol, monostearate of glycerol, monomethyl ether of glycerol, pentaerythritol, 9,10-dihydroxy stearic acid, methyl ester of 9,10-dihydroxy stearic acid, 1,2- butanediol, 2,3-hexanediol, 2,4-hexanediol, pinacol, erythritol, arabitol, sorbitol, mannitol, 1,2- cyclohexanediol, and xylene glycol. Carbohydrates such as sugars, starches, celluloses, etc., likwise may yield the esters of this invention. The carbohydrates may be exemplified by glucose, fructose; sucrose, rhamnose, mannose, glyceraldehyde, and galactose.

An expecially preferred class of polyhydric alcohols are those having at least three hydroxyl groups, such as pentaerythritol, sorbitol, mannitol, and arabitol. Soluv bility of some polyhydricalcohols may be increased by esterifying soniekof the hydroxyl groups with 'a monocarboxylic acid having from about 8 to about 30 carbon atoms such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oil acid. Examples of such-partially esterified polyhydric alcohols are the monooleate of sorbitol, distearate of sorbitol, monooleate of glycerol, monostearate of glycerol, and didodecanoate of erythritol.

The esters of this invention mayalso be derived from unsaturated alcohols such as allyl alcohol, cinnamyl alcohol, propargyl alcohol, l-cyclohexene-3-ol, and oleyl alcohol.

The aromatic hydroxy compounds from which the esters of this invention may be derived are illustrated by the following specific examples: phenol, B-naphthol, a-naphthol, cresol, resorcinol, catechol, p,p'- dihydroxybiphenyl, 2-chlorophenol, 2,4-dibutylphenol, propene tetramer-substituted phenol, didodecylphenol, 4,4'-methylene-bis-phenol, a-.decyl-B-naphthol, polyisobutene(molecular weight of 300-2,000)- substituted phenol, the condensation product of heptylphenol with 0.5 mole of formaldehyde, the condensation product of octylphenol with acetone, di(hydroxyphenyl)oxide, and 4-cyclohexylphenol. Phenol and alkylated phenols having up to three alkyl substituents are preferred. Each of the alkyl substituents may contain or more carbon atoms. I

The alkenyl halolactone monoor polyol ester reaction product will contain 0.5-5 weight percent chlorine or bromine, and its infrared spectrum will contain peaks at about 1,740 cm* (ester), 1,780 cm (lactone), and 3,450 cm (hydroxyl).

THE LUBRICANT COMPOSITIONS The lubricant compositions of this invention are prepared by blending the ester reaction product as an additive into an oil of lubricating viscosity. Suitable oils are derived from either natural or synthetic sources and generally have viscosities of from about 35 to 50,000 Saybolt Universal Seconds (SUS) at 100 F. Among natural hydrocarbonaceous oils are paraffin-base, naphthenic-base, asphaltic-base and mixed-base oils. Illustrative of synthetic oils are hydrocarbon oils such as polymers of various olefins, generally of from two to eight carbon atoms, and alkylated aromatic hydrocarbons; and nonhydrocarbon oils such as polyalkylene oxide, aromatic ethers, carboxylate esters, phosphate esters and silicon esters. The preferred media are the hydrocarbonaceous media, both natural and synthetic. The above oils may be used individually or together whenever miscible or made so by the use of mutual solvents. I

When the detergents and/or dispersants of this invention are compounded with lubricating oils for use in an engine, they will be present in a concentration of at least about 0.01 weight percent and usually not more than 20 weight percent, more usually in the range of about 0.5-15, and preferably l-lO, weight percent. Often higher concentrations are used in diesel engine lubricants than are used in gasoline engine lubricants. The compounds can also be prepared as concentrates due to their excellent compatibility with oils. As concentrates, the compounds of this invention will generally rangefrom about l0-70 weight percent, more usually.from about 20-50 weight percent of the total composition.

such as extreme pressure and antiwear agents, antioxidants, pour point depressants, oiliness agents, rust inhibitors, colorants, foam suppressants, etc. Usually, the

1,300 g. of the reaction product of Example l were mixed with 159 g. of pentaerythritol and 0.8 g. of sodium hydroxide. The reagents were stirred under a nitrogen atmosphere for 12 hours at approximately 180 total amount of these additives will range from about 5 C. The product was dissolved in mixed hexanes, al-

0.l-l5 weight percent, more usually from about 0.5-5 weight percent. The individual additives may vary from about 0.0l-5 weight percent of the composition.

In a preferred aspect, the lubricant compositions of lowed to settle and then filtered through Celite 545. The product was recovered by boiling off the hexanes and stripping under vacuum. 1,242g. of the chlorolactone pentaerythritol ester reaction product were recovthis invention will include (in addition to the ester reacl0 ered. This product contained approximately 2.6 weight tion product detergent/dispersant) l-50 mM./kg. of a dihydrocarbyl phosphorodithioate, wherein the hydrocarbyl groups are from about four to 36 carbon atoms. Usually the hydrocarbyl groups will be alkyl or alkaryl groups. The remaining valence of the phosphorodithioate will usually be satisfied by zinc, but polyalkyleneoxy or a third hydrocarbyl group may also be used. (l-lydrocarbyl" designates an organic radical composed solely of carbon and hydrogen, and which may be aliphatic, alicyclic, or aromatic.)

EXEMPLIFICATION OF THE COMPOSITIONS Example 1: Preparation of Alkenyl Chlorolactone Methyl Ester To a 3-liter flask equipped with a stirrer were charged l,300 g. of oil-free polyisobutyl succinic anhydride (in which the isobutyl portion of the molecule had a molecular weight of approximately 950), 100 cc. of methanol and 800 cc. of benzene solvent. These reagents were thoroughly mixed and then chlorine gas was bubbled through the mixture while stirring for 3 55 hours. During this period, the temperature of the reaction mixture ranged between 77 F. and 1 F. Thereafter nitrogen was bubbled through the chlorinated mixture for 10 hours and the product was recovered by stripping under vacuum. 1,397 g. of product were obtained, with a chlorine content of 4.5 weight percent. The infrared spectrum included peaks at 1,740 cm and 1,775 cm.

Although the actual reaction product is a mixture of compounds, the structures of which are not all known with certainty, it is believed that among the reactions occurring is the following:

CH2Cl CH, O

(This reaction scheme, and those elsewhere in this specification, is meant only to indicate the general nature of the reactions occurring. None is to be consid .percent of chlorine. The infrared spectrum included peaks at 1,740, 1,775, and 3,440 cm". The product had a total base number (ASTM D-664) of 32.5 (average of two runs).

As in Example 1, the reaction product will contain a 1 variety of compounds, the structures of which are not known with certainty. However, it is believed that among the reactions occurring are:

ered definitive or limiting as to structures or com- Chlorolactone Methyl Ester and 0 Incl For simplicity, only the reaction of one of the hydroxyl groups on the pentaerythritol has been shown. Obviously, there will be occurring reactions with other hydroxyl groups so that some polyesters may be formed.

Example 3: Preparation of Alkenyl Chlorolactone Acid To a l-liter flask equipped with a stirrer and heating mantle were charged 325 g. of oil-free polyisobutenyl succinic anhydride of the type described in Example l, 13 cc. of water, and 200 cc. of benzene solvent. Chlorine gas was bubbled through the mixture for about one hour. During this hour, the temperature ranged between 78 F. and l20 F. Thereafter nitrogen gas was bubbled through the chlorinated mixture for two hours and the product was recovered by stripping under vacuum. 339 g. of product were obtained, with a chlorine content of 3.9 weight percent.

As in the above examples, the exact composition of the reaction product mixture is not known with certainty. However, it is believed that among the reactions occurring is the following:

Example 4: Reaction of Pentaerythritol and Alkenyl Chlorolactone Acid 167 g. of the reaction product of Example 3 were mixed with 20 g. of pentaerythritol and 0.2 g. of NaOH. The reaction was conducted as in Example 2, to yield a product having a chlorine content of 2.27 weight percent. The infrared spectrum included peaks centered at about 1,730 cm", 1,780 cm, and 3,460 cm". The product had a total base number (ASTM D-664) of 76.5 (average of two runs). The typical reactions believed to be occurring are esterifications with water as a product analogous to the transesterifications illustrated in Example 2.

LUBRICANT COMPOSITION PERFORMANCE DATA engine of 240 in displacement with a 4.00 in. bore and a 3.18 in. stroke. The engine is operated with a Ford economy carburetor-with a manually adjustable jet in place of the power valve. Fuel and air feed rates are measured, and the air/fuel ratio controlled to 15.0 i 0.5 by adjusting the jet during Cycle 3 running (see below). The engine is run on a three-cycle test series. The conditions of each cycle are described on Table l following.

TABLE I jacket oil duration, cycle throttle RPM temp.,F. temp..F. mins. 1 ldle 750 I I 45 2 wide open 2500 125 I75 135 3 wide open 2500 170 205 60 The entire series requires 4 hours and is ordinarily run four times without cooling the engine for a 16-hour total test run. At the end of the run, the engine is disassembled and the piston skirts rated for varnish using the CRC Rating Manual No. 1. If desired, a more severe test can be obtained by repeating the l6-hour test one or more additional times. In the examples reported below in Table ll, the lubricant compositions used were composed of a hydrocarbon lubricating oil prepared by blending a 200 neutral oil, a 350 neutral oil and a 150 bright stock, and as additives, 50 mM./kg. of an overbased calcium sulfonate, l5 mM./kg. of a zinc dialkyldithiophosphate and the indicated weight percent of the test additive. The designation PBCLPE" is an abbreviation for the polyisobutenylchlorolactone pentaerythritol ester of Example 2. The designation Succinimide A refers to a commercial polyisobutenyl succinimide produced by reacting a polyisobutenyl succinic anhydride (PIBSA) with tetraethylene pentamine (TEPA). The polyisobutenyl portion of the molecule has a molecular weight of approximately 950 and the mole ratio of TEPA/PIBSA is 0.87. The designation Ester A refers to a commercial ester prepared by reacting pentaerythritol with a polyisobutenyl succinic anhydride in which the polyisobutenyl portion has a molecular weight of approximately 950-1,000.

TABLE II average piston varnish rating con.,

Scale: 040; 10 represents the cleanest piston.

These data clearly indicate that the esters of this invention are good antivarnish additives and that lubricants containing these esters are comparable in performance to lubricants containing commercial additives in their performance in automobile gasoline engines.

Example 6: I BMEP Caterpillar Diesel Engine Test The purpose of this test was to illustrate the performance of the lubricants of this invention in diesel engines. This test utilizes a single-cylinder Caterpillar supercharged diesel engine having a 5 A inches bore by 6 55 inches stroke. The engine is operated at 180 psi BMEP, a fuel input of 7,460 BTU/minute, an intake air pressure of 70 inches of mercury and a power output of 55 BHP. Other operating conditions are the same as those used in the well-known Caterpillar l-G test. The test formulation was composed of a hydrocarbon lubricating oil prepared by blending a 250 neutral oil and a 150 bright stock, mM./kg. of an overbased sulfurized calcium alkyl phenate, 2.5 mM./kg. of an overbased calcium sulfonate, 20 mM./kg. of a zinc dialkaryldithiophosphate and 6 percent of the test additive. The designation Succinimide B refers to a commercial succinimide similar to Succinimide A" above, but prepared by reaction with triethylene tetramine (TETA) instead of TEPA; the TETA/PIBSA mole ratio is 0.5. The test engine was run for hours, dismantied, and the piston inspected for groove and land deposits. Each groove is rated on a scale of 0-100, with 0 being a clean groove and 100 being a groove completely filled with deposits. Each land is rated on a scale of 0-800, with 0 being a clean land and 800 being a completely dirty land.

TABLE III Piston Ratings Dispersant Grooves Lands PBCLPE 58-8.4-0.5-0.5 220-25-20 Succinimide B 74-6.4-0.50.5 230-20-55 These data clearly indicate that the lubricants of this invention have very good performance in diesel engines and compare favorably with commercial lubricant formulations.

Example 7: Neutralization Rate Test This is a bench test designed to correlate with the well-known Sequence IlB Automobile Engine Rust Test. This test has been found to give an accurate'prediction of the performance of a given additive in the Sequence lIB test. In this test a 100 ml. solution of 0.01 N aqueous l-lCl is placed in a Beckman Expandomatic pH meter. 50 ml. of the test oil are layered into the aqueous phase and then mixed. During mixing the pH of the mixture is plotted as a function of time. The test results are reported as the number of minutes elapsed from the beginning of mixing until the curve of pl-l-versus-time shows a point of inflection; the more quickly this point of inflection occurs, the more rapidly the acid has been neutralized by the lubricant composition. The better oils, therefore, give the lowest test numbers. In the test reported below in Table IV, the test formulations were composed of a 100 neutral oil, 25 mM./kg. of the over-based calcium sulfonate of Example 6, 40 mMJkg. of the over-based sulfurized calcium alkyl phenate of, Example 6, l mM./kg. of the zinc dialkaryldithiophosphate of Example 6 and 8 percent of the test additive.

TABLE IV Time to point of Dispersant inspection; mins. PBCLPE l4.6 Succinimide A -35 Ester A 14.8

a) average of several runs b) average of two runs It is apparentfrom these data that lubricants containing the ester additives of this invention are equal in performance to lubricants containing commercial esters. Further, they are far superior in performance to lubricants containing commercial succinimides.- Example 8: L-38 Strip Corrosion Test This test is designed to evaluate a lubricant with respect to stability of resistance to oxidation, copper-lead bearing corrosion, and deposition of varnish and/or sludge on engine parts. The test is described in an article by R. W.'Jack, Lubrication, 25, 4, 37 (1970) on. page 40. The formulations used in the examples in Table V belowv all were composed of a hydrocarbon 480 neutral oil and 6 weightpercent of the test additive. The data are reported as the milligrams of copper or lead lost from the test bearings; the less corrosive loss, the better the lubricant.

It is apparent from thesedata that the lubricants containing the estersof this invention are far superior to lubricants containingthe commercial succinimides or esters in their ability to minimize corrosion.

The above data and examples are intended to be il-;

lustrative only. Those skilled in the art will be immediately aware of other embodiments within the scope and spirit of this invention.

We claim:

1. A lubricating composition comprising an oil of lubricating viscosity and from 0.01 to percent by weight of a lubricating oil additive consisting essentially of the reaction product of a monool or polyol and an alkenyl halolactone alkyl ester or acid; said ester being the reaction product of (1) an alkenyl succinic anhydride, wherein the alkenyl group has a molecular weight in the range of from 400 to 3,000, (2) a halogen selected from the group consisting of chlorine and bromine, and (3) a C -C alkanol; and said acid being the reaction-product of (I) an alkenyl succinic anhydride, wherein the alkenyl group has a molecular weight in the range of from 400 to 3,000, (2) a halogen selected from the group consisting of chlorine and bromine, and (3) water.

2. A lubricating composition according to claim 1 containing from 0.01 to 20 percent by weight of said lubricating oil additive. i V v p 3. A lubricating composition according to, claim l containing from i to IO'percent by weight of saidlubricating oil additive.

.4. A lubricating composition according to claim:l wherein said lubricating oil additive consists essentially of the reaction product of said polyol and said alkenyl halolactone alkyl ester. 7

I 5. A lubricating compositionaccording to claim 4 wherein said polyol contains at least3 hydroxyl groups, and is composed solely of carbonjhydrog'en andoxy; gen atoms. I i A 6. A lubricating composition according toclaim 5 wherein said polyol is pentaerythritol.

7. A lubricating composition according to claim 4 wherein said alkenyl group has a molecular weight in the rangefrom 700 l,400. I

8. A lubricating composition according to claim 4 wherein said halogen is chlorine.

9. A lubricating composition according to claim 4 whereinsaid C,C;, alkanol is ethanol or methanol.

10. A lubricating composition according to claim 9 wherein said C -C alkanol is methanol. I g

11. A lubricatingcomposition according to claim 1 wherein said lubricating oil additive consists essentially of the reaction product of said polyol and said alkenyl halolactone acid.

12. A lubricating composition according to claim 11 wherein saidpolyol contains at least'3 hydroxyl groups,

and is composed solely of carbon, hydrogen, and oxy-' gen atoms. v

13. A lubricating composition according to claim 12 wherein said polyol is pentaerytheitol.

the range Ioffrom'700, l ',400.

' 15.A lubricating composition according to claim 1 1 wherein said halogen is chlorine. 

2. A lubricating composition according to claim 1 containing from 0.01 to 20 percent by weight of said lubricating oil additive.
 3. A lubricating composition according to claim 1 containing from 1 to 10 percent by weight of said lubricating oil additive.
 4. A lubricating composition according to claim 1 wherein said lubricating oil additive consists essentially of the reaction product of said polyol and said alkenyl halolactone alkyl ester.
 5. A lubricating composition according to claim 4 wherein said polyol contains at least 3 hydroxyl groups, and is composed solely of carbon, hydrogen and oxygen atoms.
 6. A lubricating composition according to claim 5 wherein said polyol is pentaerythritol.
 7. A lubricating composition according to claim 4 wherein said alkenyl group has a molecular weight in the range from 700-1,400.
 8. A lubricating composition according to claim 4 wherein said halogen is chlorine.
 9. A lubricating composition according to claim 4 wherein said C1-C3 alkanol is ethanol or methanol.
 10. A lubricating composition according to claim 9 wherein said C1-C3 alkanol is methanol.
 11. A lubricating composition according to claim 1 wherein said lubricating oil additive consists essentially of the reaction product of said polyol and said alkenyl halolactone acid.
 12. A lubricating composition according to claim 11 wherein said polyol contains at least 3 hydroxyl groups, and is composed solely of carbon, hydrogen, and oxygen atoms.
 13. A lubricating composition according to claim 12 wherein said polyol is pentaerytheitol.
 14. A lubricating composition according to claim 11 wherein said alkenyl group has a molecular weight in the range of from 700-1,
 400. 15. A lubricating composition according to claim 11 wherein said halogen is chlorine. 